Pyridine recovery process



Patented Jan. 29, 1946 UNITED STATES PATENT OFFICE PYRIDINE RECOVERY PROCESS Bernard I. 0. van der Hoeven, Pittsburgh, Pa., assignor, by mes ne assignments, to Kappers Company, 1110., a eorporation of Delaware Application December 16, 1941, Serial No. 423,195

16 Claims.

The present invention relates to the recovery of pyriciine and related bases trom aqueous acdc solutons containing the Same and especially from the acid-saturator 1iquor of a by-product coke plant.

Much of the yridine and related bases that are evolved during coal carbonization and especially an important portion of pyridine, itself, is present in the gas passing into the acid saturator of the by-product system. These bases accumulate in the acid-saturator liquor unti1 their vapor pressure in the 1iquid is in equilibrium with that of their content in the inlet gas, whereupon they are no longer absorbed, but are expelied with the effluent gas.

The recovery method described and claime in copending application of John W. Schutt, Seria1 No. 308,237 filed December 8, 1939 (now Patent No. 2,311134 issued Feb. 16, 1943), accomplishes the removal of pyridine bases from the acid saturator-liquor by neutralization and distillation of withdrawn increments thereof, by means of an excess of ammonia-still vapors containing carbon dioxide, these steps being followed by dephlegmation of the distilled vapors to reduce their water content, and thereafter by a condensation of the vapors residual to such dephlegmation, the said employed excessof ammonia-still vapors having arnmonia and carbon dioxicle contents adequate to form, with the aqueons fraction of said. condensate, a sufiiciently strong solution of a carbonate sa1t of ammonia to sa1t out therefrom anc1 gravitally segregate pyridine content thereof as a decantable upper 1ayer.

The Schutt process gives very satisfactory results where the concentration of carbon dioxide and its ratio to ammonia in the ammonia-still gases are sufficiently high to provide in the step of separating pyridine, from the aqueous condensate, an aqueous carbonate-of-ammonia solution of such concentration as wi11 maintain in substantial segregaton, from the aqueous portion, the pyridine and related bases. The ratio of carbon dioxide to ammonia in gases efiluent to coke-plant ammonia-liquor sti11s, however, varies Widely between coke-oven plants and, many times, is very W, especially when the ammoniasti1l gases inciude that ammonia of the fixed ammonia content of ammonia-liquor liberated in the limo-leg of an ammonia stil]. When this 1atter condition obtains, amongst others,- there may be in the ammonia-still vapors inlet to the pyridine-still 1ess carbon dioxide present than is required to form, with that ammonia which is in excess of the ammonia content of said vapors employed for neutralization of the saturator iiquor, a carbonate sa1t in suficent quantity to eiect satisfactory separation of pyridine from the condensed steam required to volatiiize the pyridine from the pyridine-still, and the subscqnent gravital separation of the pyridine and the carbonate-of-ammonia so1ution is rendered iess satsfactcry and may be very ciifiicult by reason of free ammonia dissolved in the aqueous solution, whereby ts densitycan be lowered to such an extent that it will no longer float the pyridine.

This presence of dissolved free ammonia can be itse1f avoided by the simple expedients of flowing, ammonia-still vapors to the neutralization and distillation step in a quantity such that there remains, residual to the neutralization of the saturator iiquor, on1y enough ammonia to be stoichiometrically equivalent to the relativeiy 10W concentraton of carbon dioxide introduced there with and, of supplying, if necessary, such addi tional heat for the pyridine distillation in the form of direct or indirect steam instead of reiying on additional ammonia-still iapors fox distillation heat. Such procedure, however, may not provide carbon dio-Xide or ammonia in quantities that are adequate to form a sufiiciently strong solution of their sa1ts to separate pyridine from the subsequently condensed steam that is required to carry the pyridine content of the neutralized saturato-r-liquor into its condensation step.

It is an object of the present invention to provide improvements in the process as hereinabove described whereby the pyridine bases can be readi1y and economically recovered When employin-g, in its practice, ammonia-still gases that show a deficiency in carbon dioxide for the purpose.

A further object of invention is provision of simple means whereby that quantity of carbon dioxide availabie to or present within the system of said process at any given operating interval can be utilized to overcome the difficulty presented by its insuficient concentration in the vapors and gases normally effluent to the ammonia still of the associated coke plant.

The invention has for further objects such other improvements and such other operative advantages or results as may be found to obtain in the processes or apparatus hereinafter described or claimed.

By means of the instant improvement, ammonia-still gases and vapors, wherein the carbon dioxide is so 10W that their direct employment in the pyridine-recovery process as delineated in the above-mentioned copending applicaton (now Patent No. 2,311134) precludes satisfactory separation of pyridine and related bases from the aqueous fraction of the dstilled pyridine condensate, can still serve as the source for the ammonia and the carbon doxide that are contnuously flowed into and, in art,entirely throu h the pyridine-recovery system.

The present invention provides for inflows of ammonia and carbon dioxide into the pyridinedistillation zone at preadjusted rates that are correlated to the simultaneous inflow of pyridine-hearing acidic liquor, the rate of infiow of carbon dioxide being suficient that ts absorption and conversion to carbonate of ammonia in the condensed steam, that is required to remove pyridine-base from said pyridine-distillaton zone and to carry it into the condensa tion step, is adequate effectively to separate pyridine from sad condensed steam, and the rato of inflow of ammonia being such as will both liberate pyridine from acidic saturatorliquor at its rate of entry into the distillation zone and also form a carbonate salt with carbon dioxide at its said rate of inflow. The carbon dioxide and ammonia may be flowed into the pyridine-distillation zone either separately or in aclmxture. In some instances, ammonia-still vapors may contain only a slight deficiency of carbon dioxide and. the present requirements can be met by simple removal of some of their ammonia by, for example, passing the vapors through dissociator apparatus adapted to reject ammonia and water contained therewith, and thereafter flowing the vapors, so-adjusted in respect of their ratio of carbon dioxide to ammonia, directly, and without further enrichment in respect of the former, to the pyridinedistillation zone. The invention also provides for the maintaining of the required proportionate relationship between carbon dioxide and ammonia nthose instanceswhere there is such deficiency of carbon dioxide of the ammoniastill vapors that even those vapors flowed through dissociator apparatus are unsuted for the present purpose, by reusing the active components of that carbonate of ammonia prevously collected in the condensation step of the proe ess. Such reusng of ammonia and carbon dioxide can be accomplished by recycling carbonate-of-ammoniasolution from the condensation step to the pyridine-distillation zone either directly, or by previously volatilizing its active components in, for example, the ammonia still and retaining the carbon dioxide thereof in the system by means of said dissociator apparatus, or by extraneously revolatilizng its activa components in an auxiliary still and delivering them to the said distillation zone. It is obvious that by said recycling of carbon dioxde and ammonia that the only additional ammonia requirement in the practice of the process is for the libera tion of pyridine bases from the infio-wng acid saturator lquor which can, of course, have its source in ammonia-still vapors of any composition. Contnuous recycling of the active components of carbonate of ammonia from the condensation step to the pyrclina-distillation zone makes it a simple matter, by such entrapment of, especially, carbon dioxide within the process system, to maintain any preferred degree of concentration of these said components in the aqueous condensate.

The accompanying drawing forming a part of this specification and sh0wing for purposes of exemplification a preferred apparatus and meth- 0d in which the invention may be embodied and practiced but without limiting the claimed invention specifica11y to such illustratve instance or instances, is a diagrammatic elevational view of apparatus for the continuous recovery of pyridine bases in accordance with the present invention.

Ammoniaand. pyridine-hearing coke-oven gas is flowed through gas inlet 3 into ammonia saturator 5 and is scrubbed by an acid-actuator bath therein. The gas substantially free of said ammonia and pyridine leaves the saturator through gas outlet 4. Saturator bath liquor is withdrawn therefrom either continuously or intermittently and at a rato to prevent loss to the sa1t or to the efiiuent gas, of pyridine and related bases. The so-wthdrawn liquor after having been freed of its solid ammonium sulphate by means of salt table 6 and settling tank 1 is thereafter delivered to pyridine-neutralizing still 8 through pipe 9. Herein the free pyridine bases are liberated by neutralization of said liquor by the introduction of ammonia-still vapors emitting from perforated distributor pipe lil and are distilled therefrom by the heat of said neutralization that, optionally, can be augmented by the heat of indirect steam supplied to steam coil ll. Depyridinized liquor is withclrawn from pyridine still 8 through seal I2 and is delivered to settlng tank 13 and filtering means [4 for the removal of solids present in the said liquor and especially of sulphides formed by reaction of saturator-liquor contaminants with hydrogen sulphide, a1so present in the ammoniastill gas. The so-clarified liquor is thereafter returned to the ammonia saturator through pipe I5.

Ammonia-lquor still |6 that is provided with ammonia liquor inlet and dissociator |8 produces the ammonia-still gases that are supplied through pyridine still feed line |9 and the hereinabove mentioned perforated distributor-pipe I!) in pyridine still 8 for the neutralization of the said saturator liquor and for the distillation of pyridine therefrom. Vaporized pyridine, the ammonia residual to neutralization, the carbon dioxide, and the steam of the ammonia-still vapors are dephlegmated in partial-condenser apparatus 20 therefor in a manner as described in the abovementioned. copending application and for the purpose of increasing the concentration of ammonium carbonate in the subsequent condensate. The dephlegmated vapors are condensed in condenser 2I and any fixed gases present therein are allowed to escape through vent 22. The condensate comprising pyridine and ammonium carbonate solution fiows through pipe 23 into a sep arator 24, for separation into two liquid phases,

a lighter supernatant pyridine layer and a denser,

concentrated ammonium carbonate solution. The so-separated partially dehydrated pyridine is decanted through pipe 25 to pyridine storage tank 26, that is equipped with an elevated outlet 21 and with a drain line 28 or removing further quantities of water by separation. While this separation can be, as hereinbefore discussed, reaclily accomplisheol by the method of the Schutt inventon when the carbon dioxide to ammonia ratio of the ammonia-still gases is of the correct value, separaton of pyridine is extremely diificult and often practically infeasible when a great excess of ammonia occurs therein, and the carbon dioxde content is 10W.

The present invention solves this dfflculty in smple and novel manner by entrapping carbon dioxide, originally delivered in insufllcient relative quantity to the pyridine still within a cycle comprising the distillaton, the condensation, and the gravital separation steps of the described process, said entrapment beng accomplished to the pyridine still carbon doxide in concentration substantially stochiometrically equivalent to residual ammonia also present in said vapors.

Ammonium carbonate solution, so-returned to the pyridine still, furnishes the distillation step with a source of ammonia and carbon dioxide of which the former has been diminished in relatve quantity by the aforementioned neutralization of acid saturator-bath liquor. that, while the ammonium carbonate solution initially recycled to the pyridine still can contain dissolved ammonia, it is soon reduced and eventually elimnated by repeated neutralization of the acid liquor. Thereafter, the flow of ammonia-still vapors to the pyridine still needs to bemaintained, only at that rate supplying sufficient ammonia to neutralize the acid bath and to react with that relatively small amount of carbon dioxide carried along therewith. Introduction of this flow of still vapors to the pyridine still will, of course, continue to produce additional ammonium carbonate at a rate stoichiometrically equivalent to the rate of carbon olioxide additions thereto. such accumulated ammonium carbonate solution can be returned to the ammonia-liquor still or can be delivered to any preferred apparatus, by the opening of valv 3I in drain line 32.

It is to be noted in operation of the present improvement that, even thbugh the nflow of ammonia-still vapors may be decreased to substantially merely that rate providing neutralization of the simultaneous inflow of saturator-bath liquor and liberation of the pyridine bases contained therein, nevertheless an equal volume of acid saturator-bath lquor is neutralized at the same rate as when a great excesg of ammonia-still vapors is employed, and thus the same total heat of neutralization is obtained. If, however, it is desired to avoid the use of indirect steam supplied to the said steam coil H, when such is needed in order to revaporize the returned ammonium carbonate solution, the solution can be returned instead by pump 33 from pipe 29 and through line 34 to the aforementioned dissociator l8, wherein the solution can be revaporized and returneol to the neutralzing still 8 through pipe |9 or the solution can be vaporized in extraneous apparatus and even dephlegmated extraneously in order partially to dehy drate the vaporized ammonium carbonate constituents before their return to the vapors eiiiuent to the pyridine still.

In starting up operation of the process, a certain time of recycling will be required until sufficient ammonia and carbon dioxide have been collected in solution to produce a good separaton. In these special circumstances where the It can be seen therefore,

carbon .dioxide content is extremely low, this starting up period may be excessively long, or, although the pyridine bases can be distilled from the saturator lquor, they may be, for a wastefully long time, unobtainable in that readily decantable form that is ordinarily provided by their gravital segregation from an aqueous carbonateof-ammonia solution of requisite concentration and density.

Provision is therefore made, in the present invention, of a method for directly preadjusting the proportionate inflows of ammonia and carbon dioxide to the pyridine still, said method being, in addition to its important general utility, of special application or initiation of the processoperation in. such as the hereinabove described case where the ammonia-still gases are extremely deficient in carbon dioxide, and where the hereinabove described improvement of recycling carbonate-of-ammonia solution is cooperatively employed. Such preadjustment of the ratio of carbon dioxlde to ammonia in the ammonia-still vapors is accomplished by a partial condensation of the latter in a dissociator I8, of conventional design, that is disposed atop the amrnonia still I and. is connected therewith by pipe 35. The dissociator is supplied with indirect cooling means, the cooling water being receivecl and discharged through pipes 36 and 31 respectively. By means of the said dissociator ammonia and water, that are present in ammonia-still vapors immediately effluent to the ammonia still, can be refiuxed to the still column, and an ammonia-stillgas with an increased carbon dioxio'le to ammonia ratio can thus be flowed directly to the pyridine still 8 through vapor line 38 and the still feed line I9 to which line the former connects. So-treated ammonia-still vapors that are effluent to the dissociator and that have a higher ratio of carbon dioxide to ammonia than that of the original ammonia-still vapors can also be blended With a stream of the latter flowing directly from the ammonia still by adjustment of valve 39 in vapor line 38 and of valve 40 in still feed line |9. Those ammoniastill vapors not employed in operation of the pyridine-neutralizing still are deliverecl to the gas inlet of the saturator 5 through ammonia-still vapor line 4! at a rate that is governed by adjustment of valve 42 disposed therein.

Where the required increase in the ratio of carbon dioxide to ammonia in the ammonia-still vapors is not graat, the dissociator |8 can be employed alone to provide the proper proportonate infiows of ammonia and carbon dioxide to the pyridine still. In such operation, subsequently condensed ammonium carbonate solution need not, of course, be returned to the pyridine-distillation zone.

In that optional method for the recirculation of ammonium carbonate solution -which comprises flowing it as hereinbefore described through means including pipe 34 to the said dissociator l8, the solution canbe itself employed as a direct cooling means in the dissociator and in turn, can be evaporated therein. By such optional operation, ammonium carbonate solution is, as aforen1entioned, vaporized before delivery to the pyridine still and thereby possible dilution of the pyricline bases in the still contents is avoided. In many cases, however, the arnmonium carbonate solution from the separator will contain a high enough concentration of pyridine bases that very little, any, dilution will occur even though direct recycling of ammonium carbonate solution is employed. In addition, the described delivery of ammonium carbonate solution in vaporized form serves, along with the heat of neutrali'zatmn ofthe saturator liquor, toprovde the heat for disti11aton thereby avoidng possible need for the auxiliary use of indirect steam.

In the absence of a dissociator it is in many instanoes possible to conserve much of the carbon dioxide component of the ammonium carbonate soluton by returnng the separated aqueous solution directly to the ammonia sti11. Such operation would be applicable on1y when most of tilling from such mixture pyridne base and. aqueous vapors along with some ammonia and carbon dioxide, and condensing these sad distilled constituents in the presence of each other to form an aqueous solution of a carbonate sa1t of ammonia that will gravtatively separate the pyridine bases therefrom as a supernatant layer of pyridine-base concentrate, the improvement comprising, recycling carbonate sa1t of ammonia previousiy collected in sad condensation step into sad pyridine distillation zone by distillng, separately from the ammonia-liquor from which the ammonia sti11 vapors are derived, aqueous soluton of sad sa1t that is wthdrawn from sad condensation step and fiowing the resultant ammonia and carbon dioxide vapors into sad pyridine distiilation zone, thereby to ensure in sad condensation step the presence of sufficient of sad sa1t to mantain the density of the condensate at a value sufiiciently high to effect the aforesaid gravitational separation of a supernatant layer of pyridine base adequately and easily in those instances where the sad ammoniasti1l vapors would otherwise contain a deficiency of carbon dioxide fox that purpose.

2. In a process for recoverng pyrdine bases from saturator-bath liquor of ammonium sulphate containing the same, which comprises, fiowing sad saturator-bath liquor and ammoniastil1 vapors into a pyridine distillation zone, disti1ling from such mixture pyridine base and aqueous vapors along with some ammonia and carbon dioxide, and condensing these sad distilled constituents in the presence of each other to form an aqueous solution of a carbonate sa1t of ammonia that will gravitately separate the pyridine bases therefrom as a supernatant 1ayer of pyridine-base concentrate, the improvement comprising, recycling carbonate sa1t of ammonia previously collected. in sad condensation step by distilling aqueous solution thereof withdrawn from sad condensation step into the aforementioned. ammonia-stiil vapors, thereafter flowing resultant vaporous mixture into a dissocation step and dissociatng from the vaporous mixture and retaining therein a portion of their ammonia content wh1e passing substantially all the carbon doxide content and therein increasng the ratio of carbon dioxide te ammonia in ammoniastill vapors, before the 1atte1 enters sad pyridine distillation zone to a ratio which will maintan'the density of the aqueous prtion fromthe condensing step at a value suficiently high 'to effect the aforesaid. gravitational separation of pyrdine bases adequatey and easily.

3. In a process for recovering pyridine bases, from saturator-bath liquor of ammonum sulphate containing the same, which process comprises, fiowing sad saturator-bath liquor and. ammonia-still vapors into a pyridine distillation zone, distilling from such mixture both pyridine base and aqueous vapors, thereafter condensing them in the presence of each other, sad ammonia-still vapors normally containing a ratio of carbon dioxide to ammonia less than can supp1y to the sad pyridine base andaqueous vapors at their rates of distillation sufficent carbonate sa1t of ammonia to effect by solutionin the aqueous portion of sad distillation vapors upon their condensation a substantial gravitational segregation of pyrdine base from sad aqueous portion, the improvement comprising, decreasing the ratio of ammonia to carbon dioxide in sad ammonia-still vapors, durng their fiow from their ammonia-still to said pyridine distillation zone, relative to that which existed in the vapors as they issued from the liquor in their still, to such proportionate relationship that the resultant vapors contain, when they flow into sad pyridine distillaton zone, substantially merely suficient ammonia both to liberate pyridine base from the inflowing saturator-bath liquor and to form with the carbon dioxide content of the vapors such a quantity of a carbonate sa1t of ammonia that after sad. distillation and sad condensation the density of sad aqueous portion will be of a value sufficiently high to automatically separate the pyridine bases from sad aqueous portion as a supernatant layer of pyridine-base concentrate adequately and easily by gravitational separation.

4. In a process for recovering pyridine bases from saturator-bath liquor of ammonium sulphate containing the same, which comprises flowing such saturator-bath liquor and also ammoniasti1l vapors into a pyridine distillation zone, distillng from the resultant mixture both pyridine base and aqueous vapors, thereafter condensing them in the presence of each other, sad ammonia-still vapors normally containing a ratio of carbon dioxide to ammonia less than can supp1y to the sad pyridine base and aqueous vapors at their rate of distillaton suficient carbonate sa1t of ammonia to effect, by its solution in the aqueous portion of sad pyridine distillation vapors, upon their condensaton, a substantial segregation of pyridine base from sad aqueous portion by gravitational separation, the improvement comprising, decreasing the ratio of ammonia to carbon dioxide in sad ammona-still vapors by flowing them into dissociator apparatus that is operative to retain a porton of their ammonia content and to permit passage of substantially al1 their carbon dioxde content, and in sad. dissociator apparatus dissociating from the vapors and retainng therein the portion of the ammonia content of sad vapors in excess of that required for establishing in the ammoniasti11 vapors efflu'ent to sad dissociation apparatus such proportionate relationship of the carbon dioxide to ammonia in the contents of the efiluent vapors prior to their flow nto sad pyridine distillation zone, that sad efiiuent vapors from the dissociating step contain substantially mere1y suflicient ammonia both to liberate pyridine base from the saturator-bath liquor in the pyridine distillation Zone and to form wth the carbon dioxide content of the efiiuent vapors a carbonate sa1t of ammonia in amount such that during the subsequent condensation the latter dissolves in the aqueous portion of the condensate in an amount suficent to maintain the density of said aqueous portion at a value suficiently high to automatically separate the pyridine base from said aqueous portion as a supernatant layer of pyridine-base concentrate by gravitational separation adequately and easily.

5. In a process for recoverng pyrdine bases from saturator-bath 1quor of ammonium sulphate containing the same, which comprises, flowing said saturator-bath 1iquor and ammoniasti11 vapors into a pyridine distillation zone, distilling from such mixture pyrdine base and. aqueons vapors along with some ammonia and carbon dioxide, and condensing these said distilled constituents in the presence of each other to form an aqueous solution of a carbonate sa1t of ammonia that will gravitatively separate the pyridine bases therefrom as a supernatant layer of pyridine-base concentrate, the improvement comprisng, flowing the vapors from the ammonia still that are to be passed into said pyridine distillaton zone through a dissociator apparatus and dissocating from the vapors and retaining therain a porton of ther ammonia content While passing substantially all of their carbon dioxide content, and thereby increasing the ratio of carbon dioxide to ammonia in the ammonia-stll vapors prior to ther introduction into said distillaton zone, and. recycling carbonate sa1t of ammonia previously collected. in said condensation step to a prior dstillation step in the process so that its components are volatilized into the process in such manner that the ammonia and carbon dioxide thereof mixes with only those vapors from the ammonia still that are to be passed into said pyridine distllaton zone, and issue from said pyridine distllaton zone, in admixture with new quantities of pyridine base from the saturator-bath 1iquor and aqueous vaperfrom the dissociator in amounts such that, together, the dissociating step and the recycling step ensure in said. condensation step the presence of sufficient carbonate sa1t of ammonia in solution in the aqueous condensate to mantain its density at a value suflciently high to effect the aforesaid gravitational separaton of a supernatant 1ayer of pyrdne base adequately and easi1y in those instances where the vapors from the ammonia-still, after passing through, without use of the dssociating and recycling steps, would otherwise contain a deficiency of carbon dioxide for the purpose.

6. A method as clamed. in claim 2, and in which the carbonate salt of ammonia is recycied into the ammonia-still.

'7. A method as claimed in claim 5, and in which the carbonate sa1t of ammonia is recycled into the dissociator step.

8. A method as claimed in claim 5, and in which the carbonate salt of ammonia is recycled into the said distlling zone.

9. In a process for recovering pyrdne base from saturator-bath liquor of ammonium sulphate, which process comprises: flowing saturator-bath lquor and ammonia-still vapors into a distillation zone, distlling from such mixture pyridine base and aqueous vapor along wth ammonia and carbon doxde, and condensng said distilled consttuents in the presence of each other to form an aqueous solution of a carbonate salt of ammonia that will gravitatively separate the pyridine base therefrom as a supernatant layer of pyrdine base concentrate, the improvement comprising; fiowng the vapors from the ammonia stl1, that are to be passed into said distillation zone, into dissociation step and. dissocating from said vapors and retaining therein a portion of ther ammonia content while passing substantally all of their carbon dioxde content, thereby ncreasing the ratio of carbon dioxide to ammonia in the ammohia-still vapors prior to their introduction into said distillaton zone, to ensure an absence of an excess of ammonia over that for neutralization in the distillation zone and for forming a solution of carbonate sa1t of ammonia in sufficient quantity in the aqueous condensate to maintain its density at a value suficiently high to eect the aforesaid gravital separaton of the pyridine bases as a supernatant layer of Dyridine base concentrate adequately and easily.

10. In a process for recovering pyridine bases from saturator-bath 1iquor of ammonium sulphate, which process comprises: flowing saturator-bath liquor and ammonia-still vapors into a pyridine distillation zone, distilling from such mixture pyridine base and aqueous vapor along with ammonia and. carbon dioxide, and condensng said distilled constituents in the presence of each other to form an aqueous solution of a carbonate sa1t of ammonia that will gravtatively separate the pyridine bases therefrom as 2. supernatant 1ayer of pyridin base concentrate, the improvement comprising; fiowing a portion on1y of the vapors from an ammonia sti11 into the pyrdine distillng zone, and recycling carbonate sa1t of ammonia previously collected in said condensaton step so that its components are volatilzed into the process in such manner that the carbon dioxide thereof mixes wth on1y those vapors from the ammonia-still that are to be passed into said pyrdine distillation zone, and. issue from said pyridine distlling zone in admixture wth new quantites of pyridine base from the saturation-bath lquor and the aqueous vapor from the ammonia sti1l in amount such that, together, the vapor flow from the sti1l and the recycling step ensure that nthe condensation step enough of the ammonia present therein is combined in the form of a solution of a carbcnate salt of ammonia in the aqueous condensate to maintan the density of the aqueous condensate at a value suficiently high to effect the aforesaid gravtational separation of the pyrdine bases as a supernatant layer of pyridine base concentrate adequately and easily.

11. In a process of recoverng pyridine base from coke-plant ammonum-sulphate saturator lquor containing the same, said process comprising: flowing saturator 1iquor aforesaid and part of the wet ammona-still vapors of said coke plant together into a pyrdine-base distil- 1ation zone, with passage of some of said wet ammonia-still vapors and the dstilled pyridinebase vapors therefrom, followed by their condensation in the presence of each other, the improvement comprising; for such coke-plant ammonia-still vapors as natively contain such high ratio of ammonia to carbon dioxide, when fiowed directly from the coke plant ammonia still directly into the pyridine-base distllation zone, that ammonium carbonate faiIs of formation in the aforesaid condensation step in sufficient quantty to effect adequate and easy gravitational separation of the condensed pyridine base from the aqueous porton of the condensate,

preadjusting the carbon dioxide concentration in the stream of those ammona-still vapors that are to be flowed into the pyridine distiilation zone relative to that whch existed in the vapors as they issued from the 1iquor in the ammonia sti1l, after separation of said vapors from the remaining part of the sti11 vapors but prior to their admixture with said saturator liquor, until their carbon dioxide content is sufiicientiy high that after their neutralization of the saturator liquor, and liberation of pyridine from the latter, the remaining said wet vapors passing to the said condensation step along with pyridine-base vapor distilled from said liquor have a carbon dioxide-to-ammonia ratio that is at least substantially about said ratio in ammonium carbonate, and smultaneously condensing said remaining wet stil1 vapors and pyridine vapors in the presence of each other thereby forming aqueous solution of ammonium carbonate in the condensation step and. inhibiting the otherwise dissolution of so-condensed pyridine base in the aqneous portion of said condensate.

12. A process as claimed. in claim 11 and in which those ammonia-still vapors that are fiowed into admixture with the saturator 1iquor are preadjusted in respect of theii carbon dioxde concentration as aforesaid by flowing saidvapors through a cooling zone after their withdrawal from the ammonia-still and. prior to their admixture with the saturator liquor, and maintainng said cooling zone at a temperature suficiently low selectively to remove ammonia from sad vapors by dissocaton ther'efrom but sufiiciently high to enrch the carbon dioxide concentration in the vapor efliuent to said cooling zone.

13. A process as claimed in claim 11 and in which those ammonia-still vapors that are fiowed into admixture with the saturator 1iquor are preadjusted in respect of their carbon dioxde concentration as aforesaid by blending therewith, after their separation from the remaining part of the sti11 vapors from the sti11 but prior to their introduction into the pyridine -base dstillation zone, ammonia and carbon dioxide derived from ammonium carbonate previously condensed in the Said condensation step.

14. In a process for recovering py ridine base from coke-plant ammonium-sulphate saturator liquor containing the same,said process comprising flowng saturator 1iquor aforesaid and part of the wet ammonia-still vapors of said coke plant together into a pyridine-distillation zone, with passage of some of said wet ammonia-still vapors and the distilledpyridine base from said zone followed by their condensation and separation in the presence of each other, the improvement comprising, for such part of the coke-plant ammonia-still vapors as upon delivery directly from the coke-plant ammonia-still direct1y into the pyridine-base distillation zone fail, regard- 1ess of their concentration of ammonia even upon extensive dephlegmation of these said ammonia-still vapors that pass with the pyridine from its distillation zone, gravtatively to separate condensed pyridine from aqueous condensate, increasing the carbon dioxide content of the part of the ammona-still vapors fiowing through said pyridine-recovery process system relative to that which existed in the vapors as they issued from the 1iqnor in the ammonia st1l, between their point of entry into andtheir condensation in the presence of distilledpyridine in the pyridine recovery system, by a step providing carbon dioxide in at least about substantially stoichometric ratio to the ammonia thereof entering said condensation step and thereby causing pyridineto separate in a phase separate from the aqueous fraction of condensed condensate.

15. A process as c1aimed in claim 14 and wherein the carbon dioxide employed for establishing the said stoichiometric ratio between carbon dioxide and ammonia is derived by re-vaporzing into said process system ammonium carbonate recovered from the step of pyridine condensation and separation.

16. A process as clamed in claim 1, and in wh ich the carbonate of ammoniasoluton from the condensation step is recycled. directly into said pyridine dstillation zone and. distilled therein.

BERNARD J. C. VAN DER HOEVEN. 

